CN104203571A

CN104203571A - Method for producing laminate film containing liquid crystalline compound having high crystallinity

Info

Publication number: CN104203571A
Application number: CN201380017491.4A
Authority: CN
Inventors: 池田怜男奈; 网盛一郎
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2012-03-30
Filing date: 2013-03-28
Publication date: 2014-12-10
Also published as: US20150017423A1; JP2013208882A; WO2013146981A1

Abstract

The present invention provides a method that is for producing a laminate film and that that includes forming a layer by curing a liquid crystalline composition containing a liquid crystalline compound having a polymerizable group and that is solid at 25 DEG C, and forming a polymer layer on the layer from a composition containing a polymer, such that after forming the polymer layer, the liquid crystalline compound migrates into the polymer layer until becoming 0.1-30 mass% of the solid content mass of the polymer layer. The production method includes selecting the polymer and the liquid crystalline compound from combinations having a heat of crystallization of the mixture resulting from mixing the two at a mass ratio of 9:10 of no greater than 0.75 J/g. The method has the advantage that it is difficult for white cloudiness to arise alongside crystallization of the liquid crystalline compound.

Description

The manufacture method of the stack membrane that contains the liquid crystal compounds that crystallinity is high

[technical field]

The manufacture method of the stack membrane that the present invention relates to contain the liquid crystal compounds that crystallinity is high.In more detail, the present invention relates to a kind of manufacture method of stack membrane, it is included in the upper operation that forms polymeric layer of the layer being formed by the composition that contains the liquid crystal compounds that crystallinity is high, and this manufacture method can suppress the crystallization of above-mentioned liquid crystal compounds.

[background technology]

The layer that the composition that contains liquid crystal compounds is solidified to form has the optical anisotropy being brought by the orientation form of liquid crystal liquid crystal property molecule.Further stacked polymeric layer on the optical anisotropic layer forming like this, can provide multiple stack membrane.

In the situation that the composition that on optical anisotropic layer, coated polymeric layer is made use forms stack membrane as described above, observe liquid crystal compounds and move in polymeric layer and with the form of crystallization and separate out, produce muddy situation.As the means of avoiding the crystallization of liquid crystal compounds, seen in patent documentation 1～5, carried out changing the research of the structure of the compound that crystallinity is high in the past.It is effective that crystallization about a few hours in manufacturing process when crystallization based on structural change suppresses for solution coat for example and so on suppresses.But, the goods after solution coat are for example preserved above long-term like this crystallization in 24 hours suppress in and to no effect.Further, even if liquid crystal compounds has separately the structure that can effectively suppress crystallization, but while coexisting with polymer, its crystallinity may change, lose crystallization inhibition.Thereby, in the combination with multiple polymers layer, in its research, need to carry out the structure that a large amount of work changes liquid crystal compounds, even also can there is not crystallization so that it moves in these layers.

[prior art document]

[patent documentation]

Patent documentation 1: TOHKEMY 2005-272560 communique

Patent documentation 2:WO2008/026482 communique

Patent documentation 3: TOHKEMY 2003-192645 communique

Patent documentation 4: Japanese kokai publication hei 7-41758 communique

Patent documentation 5: Japanese kokai publication hei 11-288110 communique

[summary of the invention]

[inventing problem to be solved]

Problem of the present invention is to provide a kind of manufacture method of stack membrane, as being included in the upper manufacture method that forms the stack membrane of polymeric layer of the layer being formed by the liquid crystalline composition that contains high crystalline liquid crystal compounds, the muddiness that its crystallization that is not easy generation and liquid crystal compounds accompanies.

[solving the means of problem]

The inventor's the starting point is, the crystallization easiness of liquid crystal compounds not only depends on the crystallinity of liquid crystal compounds but also depends on the polymer of the stacked polymeric layer of formation, attempts whether utilizing both find out the index that crystallization occurs in the related parameter.It found that, the crystallization heat of both mixtures and crystallization there is dependency relation, thereby completed the present invention.

That is, the invention provides following (1)～(13).

(1) manufacture method for stack membrane, it comprises:

By containing, there is polymerizable group and at 25 ℃, be the liquid crystal compounds of solid liquid crystalline composition solidifies to form layer; And by the composition that contains polymer, form polymeric layer on above-mentioned layer;

After above-mentioned polymeric layer forms, above-mentioned liquid crystal compounds moves in above-mentioned polymeric layer, until its solid constituent quality with respect to above-mentioned polymeric layer reaches 0.1 quality %～30 quality %;

Wherein, this manufacture method comprises selects above-mentioned liquid crystal compounds and above-mentioned polymer from following combination, and this is combined as take the combination below 0.75J/g of the crystallization heat of the mixture that mass ratio 9:10 is mixed to get by above-mentioned liquid crystal compounds and above-mentioned polymer.

(2) manufacture method as described in (1), wherein, is directly coated on the above-mentioned composition that contains polymer on the layer that above-mentioned liquid crystalline composition is solidify to form.

(3) manufacture method as described in (1) or (2), wherein, after above-mentioned polymeric layer forms, above-mentioned liquid crystal compounds moves in above-mentioned polymeric layer, until its solid constituent quality with respect to above-mentioned polymeric layer reaches 1 quality %～20 quality %.

(4) manufacture method as described in any one of (1)～(3), wherein, above-mentioned solidifying by carrying out based on light-struck polymerisation.

(5) manufacture method as described in any one of (1)～(4), wherein, the above-mentioned composition that contains polymer is coated with the form of the solution of following solvents, and this solvent is selected from alkyl halide ester keto-alcohol glycol ethers or their mixture.

(6) manufacture method as described in (5), wherein, the above-mentioned composition that contains polymer is coated with the form of the solution of following solvents, and this solvent is selected from acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, methyl alcohol, ethanol, isopropyl alcohol, butanols, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or their mixture.

(7) stack membrane, it is manufactured by the manufacture method described in any one of (1)～(6).

(8) stack membrane, it sequentially comprises the layer being formed by the liquid crystalline composition that contains the liquid crystal compounds with polymerizable group and the polymeric layer being formed by the composition that contains polymer, wherein,

In above-mentioned polymeric layer, with respect to the solid constituent quality of above-mentioned polymeric layer, above-mentioned liquid crystal compounds contains 0.1 quality %～30 quality %;

Above-mentioned liquid crystal compounds is to be the compound of solid at 25 ℃;

Above-mentioned liquid crystal compounds and above-mentioned polymer be take to the crystallization heat of the mixture that mass ratio 9:10 is mixed to get below 0.75J/g.

(9) stack membrane as described in (7) or (8), wherein, above-mentioned polymeric layer is optical isotropy layer.

(10) stack membrane as described in any one of (7)～(9), wherein, above-mentioned liquid crystal compounds is the rod shaped liquid crystal compound with 2 polymerizable groups, and above-mentioned polymer is copolymer, polyester, polyurethane, polystyrene, polyvinyl alcohol, EVAc, polyvinyl chloride, the cellulose derivative of poly-(methyl) methyl acrylate, (methyl) acrylic acid and (methyl) acrylate.

(11) stack membrane as described in any one of (7)～(10), wherein, above-mentioned polymer has polar group or hydrophilic radical at side chain.

(12) stack membrane as described in (11), wherein, above-mentioned polar group or hydrophilic radical are hydroxyl or carboxyl.

(13) stack membrane as described in any one of (7)～(12), wherein, the thickness of above-mentioned polymeric layer is below 10 μ m.

[effect of invention]

According to the present invention, a kind of manufacture method of stack membrane can be provided, it is to be included in the upper manufacture method that forms the stack membrane of polymeric layer of the layer being formed by the liquid crystalline composition that contains the liquid crystal compounds that crystallinity is high, and the method can be manufactured and be not easy to produce the muddy stack membrane accompanying with liquid crystal compounds crystallization.

[specific embodiment]

Below describe the present invention in detail.

It should be noted that, "～" in this description usings and comprises that the numerical value of recording before and after it is used as the implication of lower limit and higher limit.

In this manual, Re represents to postpone (phase difference).Re can be used the poor method of spectrum phase to measure, in the poor method of this spectrum phase, use Journal of Optical Society of America, vol.39, the method that p.791-794 (1949) or TOHKEMY 2008-256590 communique are recorded will through or reflection beam splitting spectrum etc. be converted into phase difference.Above-mentioned document is for use seeing through the determination method of spectrum, but particularly in the situation that of reflection, because light 2 times is by optical anisotropic layer, thereby can be using half phase difference as optical anisotropic layer of the phase difference being conversed by reflectance spectrum.When not specifying, postpone (Re) and refer to positive the delay.The value of Re (λ) for using the light of wavelength X nm to obtain as mensuration light.In this manual, Re refers to, and for R, G, B, measures the value obtaining respectively at the wavelength of 611 ± 5nm, 545 ± 5nm, 435 ± 5nm, and when not recording especially about tone, Re refers at the wavelength of 545 ± 5nm and measures the value obtaining.

In this manual, about " in fact " of angle, refer to the error of accurate angle in the be less than ± scope of 5 °.Further, be preferably less than 4 ° with the error of accurate angle, be more preferably less than 3 °.About " in fact " postponing, refer to postpone to have ± 5% with interior difference.Further, postpone to be essentially 0 and refer to that postponing is below 5nm.In addition, as long as no special Do, describe, the mensuration wavelength of refractive index refers to any wavelength of visible domain.It should be noted that, in this manual, " visible ray " refers to that wavelength is the light of 400nm～700nm.

In this manual, when being designated as " solid constituent quality ", refer to the quality of the residual component after volatile ingredient volatilization.(methyl) acrylic acid is used to comprise the implication of any one or both in acrylic acid and methacrylic acid, and (methyl) acrylate is used to comprise any one or both implications in acrylate and methacrylate.

[manufacture method of stack membrane]

Can utilize the stack membrane of manufacture method manufacture of the present invention sequentially to have: support; The layer being formed by the liquid crystalline composition that contains the liquid crystal compounds with polymerizable group; The polymeric layer being formed by the composition that contains polymer.The present invention provides a kind of in the situation that above-mentioned liquid crystal compounds especially compound that to be crystallinity high, specifically in the situation that 25 ℃ for the compound of solid, can manufacture the manufacture method of stack membrane, this stack membrane is not easy to produce by the muddiness due to liquid crystal compounds crystallization.

Between the above-mentioned layer being formed by liquid crystalline composition and above-mentioned polymeric layer, can have other layer, but in general, the layer that above-mentioned polymeric layer is obtained by the composition that directly coating contains polymer on the above-mentioned layer being formed by liquid crystalline composition forms.In manufacture method of the present invention, in above-mentioned polymeric layer in stack membrane, even in the situation that above-mentioned liquid crystal compounds with respect to the solid constituent quality of above-mentioned polymeric layer for example, with 0.1 quality %～30 quality %, exist with 1 quality %～20 quality %, also can suppress the crystallization of above-mentioned liquid crystal compounds in polymeric layer.Above-mentioned liquid crystal compounds is for example to move in above-mentioned polymeric layer in the coating at polymeric layer, stacked operation.

The inventor finds, if according to liquid crystal compounds and polymer being take to the mass ratio 9:10 (quality of liquid crystal compounds: the crystallization heat of the mixture quality of polymer) being mixed to get, as 0.75J/g selects liquid crystal compounds and polymer to get off, can not produce muddiness in the stack membrane of made.Liquid crystal compounds and polymer can be respectively mixture, in this case, take the liquid crystal compounds of form of mixtures, the polymer of form of mixtures quality is separately benchmark, by above-mentioned mass ratio by liquid crystal compounds and polymer mixed.

About the liquid crystal compounds when obtaining crystallization heat and the mixing of polymer, as long as both evenly mix, its means indefinite.As the mixture of liquid crystal compounds and polymer, for example can be by liquid crystal compounds and polymer dissolution in solvent, afterwards that this solution is solid, use dry substance.As solvent now, preferred both consoluet solvents, its kind is not particularly limited.As concrete example, can enumerate acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, methyl alcohol, ethanol, isopropyl alcohol, butanols, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or their mixture.

For obtaining the method for crystallization heat, be not particularly limited, for example, can utilize the value of using differential scanning calorimetry (DSC) to record to judge.Preferably the temperature-fall period in DSC carries out the mensuration of crystallization heat.Crystallization heat is preferably below 0.50J/g, more preferably below 0.25J/g.

[liquid crystal compounds with polymerizable group]

In manufacture method of the present invention, as liquid crystal compounds, use the material with polymerizable group.

In addition liquid crystal compounds used in forming as stack membrane, the compound that to use at 25 ℃ be solid.As such compound, for example can use take single product form while carrying out DSC the peak crystallization in temperature-fall period be more than 25 ℃ compounds.Liquid crystal compounds can be also mixture, and in this case, the liquid crystal compounds that forms mixture is solid at 25 ℃ respectively.

The molecular weight of the liquid crystal compounds in the liquid crystalline composition before curing process is generally 150～100,000 scope.Be preferably 340～50,000, more preferably 480～3,000 scope.

In general, liquid crystal compounds can be categorized as bar-shaped type and discoid type according to its shape.And then there is respectively low molecule-type and polymer electrolyte.It is more than 100 molecules (Polymer Physics phase translocation moves ダイ Na ミ Network ス (Polymer Physics phase transfer dynamics), the positive man's work of Tu Jing, 2 pages, Yan Bo bookstore, 1992) that macromolecule typically refers to the degree of polymerization.In the present invention, liquid crystal compounds all can be used arbitrarily, but preferably uses rod shaped liquid crystal compound.

It should be noted that, in this manual, when the layer forming at the composition for by containing liquid crystal compounds is described, in the layer of this formation, not must contain the compound with liquid crystal liquid crystal property.This layer is such as for containing the layer of the material that obtains as follows: above-mentioned low molecular weight liquid crystal compound has the group reacting under the effect of heat, light etc., thereby result reacts and carries out polymerization or crosslinked under the effect of heat, light etc., obtains being the material that macromolecule quantizes and lose liquid crystal liquid crystal property.As liquid crystal compounds, can use the mixture of rod shaped liquid crystal compound of more than two kinds, discoid liquid crystal compounds of more than two kinds or rod shaped liquid crystal compound and discoid liquid crystal compounds.Liquid crystal compounds preferably has 2 above polymerizable groups.In the situation that be the mixture of liquid crystal compounds of more than two kinds, at least a kind has 2 above polymerizable groups.

As polymerizable group, can enumerate vinyl, (methyl) acryloyl group, epoxy radicals, oxetanyl, vinyl ether group, hydroxyl, carboxylic acid group, amino etc.

Liquid crystal compounds has in the situation of 2 above polymerizable groups, these groups are can be all identical, can be any 2 above identical, also can be different.Also can use and there is polymerizable group of more than two kinds as the liquid crystal compounds of 2 above polymerizable groups.Can also use such liquid crystal compounds, make polymerizable group of more than two kinds crosslinked step by step, make the optically anisotropic duplexer that demonstrates pattern-like.For example, can use the combination of free-radical polymerised group and cationically polymerizable group, according to the reaction conditions such as kind of used initator, control reaction.As above-mentioned free-radical polymerised group, be vinyl or (methyl) acryloyl group and as above-mentioned cationically polymerizable group, be epoxy radicals, oxetanyl or vinyl ether group combination is easily controlled reactivity.The example of polymerizable group is shown below.

[changing 1]

As rod shaped liquid crystal compound, preferably use azomethine class, azoxy class, cyanobiphenyl class, cyano-phenyl ester class, benzoates, cyclohexane-carboxylic acid phenylester class, cyano-phenyl cyclohexanes, cyano group substituted-phenyl miazines, alkoxy substituted phenyl miazines, phenyl dioxane class, dibenzenyl (トラ Application) class and alkenyl cyclohexyl benzene formonitrile HCN class.Not only can use above-mentioned such low molecular weight liquid crystal compound, but also can use high molecule liquid crystal compound.Above-mentioned high molecule liquid crystal compound is to have the macromolecular compound that the low molecule rod shaped liquid crystal compound of reactive group is polymerized.As the example of rod shaped liquid crystal compound, can enumerate the material of recording in TOHKEMY 2008-281989 communique, No. 2008/0259268, U.S. Patent bulletin, the flat 11-513019 communique of Japanese Unexamined Patent Application Publication (International Publication WO97/00600) and Japanese Unexamined Patent Application Publication 2006-526165 communique.

Be illustrated in the concrete example of the rod shaped liquid crystal compound that 25 ℃ is solid below, but the present invention is not limited to these examples.It should be noted that, the method that following compound can be recorded with reference to the flat 11-513019 communique of Japanese Unexamined Patent Application Publication (WO97/00600) is synthesized.

[changing 2]

[changing 3]

[changing 4]

[changing 5]

[changing 6]

As liquid crystal compounds, also can use discoid liquid crystal compounds.As the example of discoid liquid crystal compounds, can enumerate: benzene derivative, be recorded in the people's such as C.Destrade research report, Mol.Cryst.71 volume, in 111 pages (1981); Three polyindenes (ト Le キセ Application) derivative, is recorded in the people's such as C.Destrade research report, Mol.Cryst.122 volume, and 141 pages (1985), Physicslett, A, 78 volumes, in 82 pages (1990); Cyclohexane derivant, is recorded in the people's such as B.Kohne research report, and Angew.Chem.96 volume, in 70 pages (1984); And aza-crown is or the large ring of phenylacetylene system, be recorded in the people's such as J.M.Lehn research report, the people's such as J.Chem.Commun.1794 page (1985), J.Zhang research report, J.Am.Chem.Soc.116 volume, in 2655 pages (1994); Etc..Above-mentioned discoid liquid crystal compounds is generally discoid parent nucleus using above-claimed cpd as minute subcenter, be aplysia punctata has the substituent structures that form such as straight chained alkyl substituting group or alkoxy substituent, substituted benzoyl oxy substituents; it demonstrates liquid crystal liquid crystal property, generally includes the compound that is called as discoid liquid crystal.Wherein, in the situation of so same orientation of molecule aggregate, demonstrate negative uniaxiality, but be not limited to this record.As the example of discoid liquid crystal compounds, can enumerate the compound of recording in paragraph [0061]～[0075] of TOHKEMY 2008-281989 communique.

With respect to the solid constituent gross mass of liquid crystalline composition, liquid crystal compounds preferably with 30 quality %～99.9 quality %, more preferably with 50 quality %～99.9 quality %, further preferably contain with 70 quality %～99.9 quality %.

The liquid crystalline composition that contains the liquid crystal compounds with polymerizable group can be solidified and carrys out making layer.For example, the liquid crystalline composition with polymerizable group of solution state can be coated on to support or be located at oriented layer on support etc. above, next be coated with layer is dry, form liquid crystalline phase, heat afterwards or irradiation by liquid crystal compounds polymerization, immobilization, carry out making layer.The thickness of the layer of made is for example 0.1 μ m～20 μ m, 0.5 μ m～10 μ m.

The layer of making is like this generally has optically anisotropic optical anisotropic layer.

[optical anisotropic layer]

Optical anisotropic layer is the layer having at least one when postponing to measure to postpone be not in fact 0 incident direction, have not for isotropic optical characteristics.Optical anisotropic layer can be for having the patterned optical anisotropic band of pattern-like birefringence.

Optical anisotropic layer more than the delay of 20 ℃ is preferably 5nm, more preferably below the above 10000nm of 10nm, most preferably be below the above 2000nm of 20nm.

Liquid crystal compounds can be fixed with the arbitrary orientation state of horizontal alignment, vertical orientated, tilted alignment and twist alignment.It should be noted that, about " horizontal alignment " in this description, the in the situation that of rod shaped liquid crystal, refer to that molecular long axis is parallel with the horizontal plane of transparent support; The in the situation that of discoid liquid crystal, refer to that the disc face of core of discoid liquid crystal compounds and the horizontal plane of transparent support are parallel, but and do not require strictly parallelly, in this manual, refer to that the inclination angle becoming with horizontal plane is less than the orientation of 10 degree.As optical anisotropic layer, preferably comprise the layer that rod shaped liquid crystal compound is obtained with being fixed of state of horizontal alignment.

Be orientated in the optical anisotropic layer that immobilization forms liquid crystalline composition being solidified to the composition form, be about to contain liquid crystal compounds, in order to promote the crosslinked of liquid crystal compounds, can add polymerizable monomer.

For example, can use and there is 2 above ethylenic unsaturated double-bonds, monomer or the oligomer that carries out addition polymerization by the irradiation of light.

As such monomer and oligomer, can enumerate and in molecule, there is at least 1 compound that can carry out the ethylenic unsaturated group of addition polymerization.As its example, can enumerate: monofunctional acrylate or the simple function methacrylates such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and (methyl) acrylic acid phenoxy ethyl, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate, ethylene oxide or propylene oxide are added to the polyfunctional acrylic esters such as compound or the multifunctional methacrylate that carries out (methyl) acroleic acid esterification after the polyfunctional alcohols such as trimethylolpropane or glycerine and obtain.

Further can enumerate: the urethane acrylate class of recording in Japanese Patent Publication 48-41708 communique, Japanese Patent Publication 50-6034 communique and Japanese kokai publication sho 51-37193 communique; The polyester acrylate class of recording in Japanese kokai publication sho 48-64183 communique, Japanese Patent Publication 49-43191 communique and Japanese Patent Publication 52-30490 communique; Epoxy resin and (methyl) acrylic acid reaction product---the polyfunctional acrylic esters such as Epoxy Acrylates or methacrylate.

Among them, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, two or five erythrite six (methyl) acrylate, two or five erythrite five (methyl) acrylate.

And then, can enumerate in addition " the polymerizable compound B " that in Japanese kokai publication hei 11-133600 communique, record as suitable compound.These monomers or oligomer can be used separately, also can be use mixing two or more.

Can use cationically polymerizable monomer in addition.Such as the epoxide exemplifying in each communiques such as No. 6-9714, No. 2001-31892, TOHKEMY, No. 2001-40068, TOHKEMY, No. 2001-55507, TOHKEMY, No. 2001-310938, TOHKEMY, No. 2001-310937, TOHKEMY, No. 2001-220526, TOHKEMY of can enumerating Japanese kokai publication hei, vinyl ether compound, oxetane compound etc.

As epoxide, can enumerate following aromatic epoxide, alicyclic epoxy thing and aliphatic epoxide etc.As aromatic epoxide, such as enumerating bisphenol-A or add diglycidyl ether or polyglycidyl ether, the hydrogenated bisphenol A of adult or add diglycidyl ether or polyglycidyl ether and the phenolic resin varnish type epoxy resin etc. of adult as its alkylene oxide as its alkylene oxide.As alkylene oxide, can enumerate oxirane and expoxy propane etc. herein.

As alicyclic epoxy thing, can enumerate by utilizing the suitable oxidant such as hydrogen peroxide, peracid to carry out to thering is the compound of the cycloalkane rings such as at least 1 cyclohexene or cyclopentene ring the compound that contains 7-oxa-bicyclo[4.1.0 or cyclopentane epoxide that epoxidation obtains.Preferred thing as aliphatic epoxide, there are aliphatic polyol or its alkylene oxide to add the diglycidyl ether of adult or polyglycidyl ether etc., as its typical example, can enumerate the diglycidyl ether of ethylene glycol, the diglycidyl ether of propane diols or 1, the diglycidyl ether of the alkylene glycols such as diglycidyl ether of 6-hexylene glycol, glycerine or its alkylene oxide add the polyglycidyl ether of the polyalcohols such as the diglycidyl ether of adult or triglycidyl ether, polyethylene glycol or its alkylene oxide add the diglycidyl ether of adult, polypropylene glycol or its alkylene oxide add the diglycidyl ether etc. of the ployalkylene glycols such as diglycidyl ether of adult.As alkylene oxide, can enumerate oxirane and expoxy propane etc. herein.

In addition,, in liquid crystalline composition, as cationically polymerizable monomer, also can use the oxetane monomer of simple function or 2 officials energy.For example, can preferably use 3-ethyl-3-hydroxymethyl oxetanes (name of an article OXT of manufacturer of Toagosei Co., Ltd 101 etc.), 1, two [(3-ethyl-3-oxetanyl) methoxy] benzene (name of an article OXT of manufacturer of Toagosei Co., Ltd 121 etc.) of 4-, 3-ethyl-3-(phenoxymethyl) oxetanes (name of an article OXT of manufacturer of Toagosei Co., Ltd 211 etc.), two (1-ethyl-3-oxetanyl) methyl ethers (name of an article OXT of manufacturer of Toagosei Co., Ltd 221 etc.), 3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes (name of an article OXT of manufacturer of Toagosei Co., Ltd 212 etc.) etc., can use especially 3-ethyl-3-hydroxymethyl oxetanes, 3-ethyl-3-(phenoxymethyl) oxetanes, compound or the TOHKEMY 2001-220526 communique of two (1-ethyl-3-oxetanyl) methyl ether etc., the whole known simple function of recording in TOHKEMY 2001-310937 communique or 2 officials can oxetane compounds.

[solvent]

In the situation that liquid crystalline composition is coated on to surperficial such as support or oriented layer described later etc. with the form of coating fluid, the solvent using in the preparation as coating fluid, preferably with an organic solvent.Example as organic solvent, can enumerate acid amides (N for example, dinethylformamide), sulfoxide (for example dimethyl sulfoxide (DMSO)), heterocyclic compound (for example pyridine), hydrocarbon (for example benzene, hexane), alkyl halide (for example chloroform, carrene), ester (for example methyl acetate, butyl acetate), ketone (for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone), ether (for example oxolane, 1,2-dimethoxy-ethane), alcohol (for example methyl alcohol, ethanol), ethylene glycol (for example propylene glycol monomethyl ether, dipropylene glycol monomethyl ether).Can mix in addition and use two or more solvents.In above-mentioned solvent, preferred alkyl halide, ester, ketone, alcohol, ethylene glycol and their mixed solvent.

[orientation immobilization]

The immobilization of the liquid crystal compounds orientation preferably cross-linking reaction of the polymerizable group by liquid crystal compounds is implemented, and more preferably by the polymerisation of polymerizable group, implements.In polymerisation, comprise the heat polymerization and the photopolymerization reaction that uses Photoepolymerizationinitiater initiater, the more preferably photopolymerization reaction that use thermal polymerization.As photopolymerization reaction, can be any one in radical polymerization, cationic polymerization.The example of radical photopolymerization initator comprises: alpha-carbonyl compound (is recorded in United States Patent (USP) No. 2367661, in each description that No. 2367670, United States Patent (USP)), acyloin ether (being recorded in No. 2448828 descriptions of United States Patent (USP)), α-hydrocarbon substituted aromatic acyloin compound (being recorded in No. 2722512 descriptions of United States Patent (USP)), multinuclear naphtoquinone compounds (is recorded in United States Patent (USP) No. 3046127, in each description that No. 2951758, United States Patent (USP)), the combination of triarylimidazoles dimer and p-aminophenyl ketone (being recorded in No. 3549367 descriptions of United States Patent (USP)), acridine and compound phenazine (are recorded in Japanese kokai publication sho 60-105667 communique, in No. 4239850 descriptions of United States Patent (USP)), Yi is Ji oxadiazole compound (being recorded in No. 4212970 descriptions of United States Patent (USP)).The example of cationic photopolymerization initator can be enumerated organic sulfonium salt system, salt compounded of iodine system, microcosmic salt system etc., preferred organic sulfonium salt system, particularly preferably triphenyl sulfonium salt.As the counter ion counterionsl gegenions of these compounds, preferably use hexafluoro antimonate, hexafluorophosphate etc.

The consumption of Photoepolymerizationinitiater initiater is preferably 0.01 quality %～20 quality % of the solid constituent of coating fluid, its 0.5 quality %～5 quality % more preferably.The polymerization irradiation used of liquid crystal compounds is preferably used ultraviolet ray.Irradiation energy is preferably 10mJ/cm ²～10J/cm ², 25mJ/cm more preferably ²～1000mJ/cm ².Illumination is preferably 10mW/cm ²～2000mW/cm ², 20mW/cm more preferably ²～1500mW/cm ², 40mW/cm more preferably ²～1000mW/cm ².As illumination wavelength, preferably at 250nm～450nm, there is peak, more preferably at 300nm～410nm, there is peak.In order to promote photopolymerization reaction, can under the inert gas atmospheres such as nitrogen or under heating condition, implement irradiation.

[horizontal alignment agent]

By contain the fluorine-containing homopolymers of the monomer of recording in paragraph " 0098 "～" 0105 " of TOHKEMY 2009-69793 communique, use the represented compound in general formula (1)～(3) and general formula (4) or at least one of copolymer in liquid crystalline composition, the molecule that can make liquid crystal compounds is horizontal alignment in fact.In the situation that making liquid crystal compounds horizontal alignment, its inclination angle be preferably 0～5 degree, more preferably 0～3 degree, more preferably 0～2 degree, most preferably be 0～1 degree.

As the addition of horizontal alignment agent, be preferably 0.01 quality %～20 quality % of the quality of liquid crystal compounds, more preferably 0.01 quality %～10 quality %, be particularly preferably 0.02 quality %～1 quality %.It should be noted that, the represented compound in general formula (1)～(4) of recording in paragraph " 0098 "～" 0105 " of TOHKEMY 2009-69793 communique can be used separately, also can share two or more.

[polymeric layer being formed by the composition that contains polymer]

The polymeric layer forming as the composition by containing polymer, such as enumerating: for the oriented layer of additional optical anisotropic layer is set, the protective layer of optical anisotropic layer, control to see through scattering of light scattering layer, prevent the damage of lower floor hard conating, prevent antistatic layer that the dust due to charged adheres to, as the printing coating layer of printed substrates, ornamental printed layers etc. is provided.Polymeric layer also can be for containing for making the layer of the polymerization initiator that the unreacted polymerizable group of optical anisotropic layer reacts.

As mentioned above, in the polymeric layer in stack membrane of the present invention, above-mentioned liquid crystal compounds contains 0.1 quality %～30 quality %.The content of this liquid crystal compounds is confirmed by the amount of existing liquid crystal compounds in the layer after layer is solidified.The content of liquid crystal compounds can be measured to confirm by the IR of cutting polymeric layer, enforcement powder.In polymeric layer, liquid crystal compounds contains to be preferably the amount of 1 quality %～20 quality %.

The thickness of polymeric layer is not particularly limited, and is that 100 μ m are following, 50 μ m are following, 15 μ m are following or the degree below 10 μ m, is that 0.1 μ m is above, 0.3 μ m is above or degree more than 0.5 μ m.

[polymer]

As polymer, be not particularly limited, can enumerate: poly-(methyl) methyl acrylate, the copolymer of (methyl) acrylic acid and (methyl) acrylic acid various esters, polystyrene, the copolymer of styrene and (methyl) acrylic acid or various (methyl) acrylate, polyvinyl alcohol, polyvinyl toluene, the copolymer of vinyltoluene and (methyl) acrylic acid or various (methyl) acrylate, styrene/ethylene base toluene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, vinyl acetate/ethylene copolymer, vinyl acetate/ethlyene dichloride copolymer, polyester, polyimides, polyurethane, polystyrene, cellulose derivative (carboxymethyl cellulose etc.), polyethylene, polypropylene and Merlon etc.As preferred example, can enumerate: the multiple copolymer of (methyl) methyl acrylate and (methyl) acrylic acid copolymer, (methyl) allyl acrylate and (methyl) acrylic acid copolymer, (methyl) benzyl acrylate and (methyl) acrylic acid and other monomer etc.These polymer can be used separately, also can be used in combination of two or more.

The molecular weight of polymer is not particularly limited, and in quality mean molecule quantity, is generally 3,000～150,000 scope.Be preferably 4,000～80,000, more preferably 5,000～30,000 scope.

With respect to the total solid composition in the composition that contains polymer, the content of polymer is generally 20 quality %～99 quality %, is preferably 40 quality %～99 quality %, 60 quality %～98 quality % more preferably.

Polymer also preferably has polar group or hydrophilic radical at side chain.It for example, for further improving its coating adaptation during stacked other functional layer (printed layers) on polymeric layer.As polar group or hydrophilic radical, be not particularly limited, as example, can enumerate amino, hydroxyl, sulfonic group, carboxyl etc., wherein preferred hydroxyl and carboxyl.

[combination of polymer and liquid crystal compounds]

About above-mentioned liquid crystal compounds and above-mentioned polymer, take the polymer of crystallization heat below 0.75J/g and the combination of liquid crystal compounds of the mixture that mass ratio 9:10 is mixed to get, for example, above-mentioned liquid crystal compounds can be selected from have the rod shaped liquid crystal compound of more than 2 polymerizable groups, and above-mentioned polymer can be selected from copolymer, polyester, polyurethane, polystyrene, polyvinyl alcohol, EVAc, polyvinyl chloride or the cellulose derivative of poly-(methyl) methyl acrylate, (methyl) acrylic acid esters various with it.

It is upper that the composition that contains polymer can directly be coated on the layer being formed by liquid crystalline composition, forms polymeric layer.The composition that contains polymer preferably, with the form coating of solution, is dried thereafter solvent evaporates, forms layer.As solvent, can enumerate organic solvent.Example as organic solvent, can enumerate: acid amides (N for example, dinethylformamide), sulfoxide (for example dimethyl sulfoxide (DMSO)), heterocyclic compound (for example pyridine), hydrocarbon (for example benzene, hexane), alkyl halide (for example chloroform, carrene), ester (for example methyl acetate, butyl acetate), ketone (for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone), ether (for example oxolane, 1,2-dimethoxy-ethane), alcohol (for example methyl alcohol, ethanol), ethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether.Also two or more solvent can be used.In above-mentioned solvent, preferred alkyl halide, ester, ketone, alcohol, ethylene glycol and their mixed solvent.

Polymeric layer can be for example photo-sensitive resin.As photo-sensitive resin, preferably contain at least one polymer and at least one Photoepolymerizationinitiater initiater.

As polymerization initiator, can enumerate thermal polymerization, Photoepolymerizationinitiater initiater etc., can correspondingly suitably use with polymerization.As Photoepolymerizationinitiater initiater, can be any in free radical Photoepolymerizationinitiater initiater, cationic Photoepolymerizationinitiater initiater.

As free radical Photoepolymerizationinitiater initiater, can enumerate: disclosed vicinal polyketone aldehyde radical (vicinal polyketaldonyl) compound in No. 2367660 description of United States Patent (USP), the acyloin ether compound of recording in No. 2448828 description of United States Patent (USP), the aromatic series acyloin compound being replaced by α-hydrocarbon of recording in No. 2722512 description of United States Patent (USP), the multinuclear naphtoquinone compounds of recording in No. 3046127 description of United States Patent (USP) and No. 2951758 description of United States Patent (USP), the triarylimidazoles dimer of recording in No. 3549367 description of United States Patent (USP) and the combination to amino ketones, the benzothiazole compound that Japanese Patent Publication 51-48516 communique is recorded and trihalomethyl s-triazine, the trihalomethyl triaizine compounds of recording in No. 4239850 description of United States Patent (USP), the San halogen Jia oxadiazole compound of recording in No. 4212976 description of United States Patent (USP) etc.Particularly preferably trihalomethyl s-triazine, San halogen Jia oxadiazole and triarylimidazoles dimer.And then, can enumerate in addition " polymerization initiator C " that Japanese kokai publication hei 11-133600 communique records as suitable initator.

As cationic photopolymerization initator, can exemplify organic sulfonium salt system, salt compounded of iodine system, microcosmic salt system etc., preferred organic sulfonium salt system, especially effective triphenyl sulfonium salt.As the counter ion counterionsl gegenions of these compounds, preferably use hexafluoro antimonate, hexafluorophosphate etc.

In addition, the amount of polymerization initiator is preferably 0.01 quality %～20 quality % of the solid constituent of the composition that contains polymer, 0.2 quality %～10 quality % more preferably.

From effectively preventing inequality, this considers on the one hand, and polymeric layer preferably contains suitable surfactant.As long as above-mentioned surfactant can mix with photosensitive polymer combination, just can use.As for preferred surfactant of the present invention, can enumerate as TOHKEMY 2003-337424 communique [0090]～[0091], TOHKEMY 2003-177522 communique [0092]～[0093], TOHKEMY 2003-177523 communique [0094]～[0095], TOHKEMY 2003-177521 communique [0096]～[0097], TOHKEMY 2003-177519 communique [0098]～[0099], TOHKEMY 2003-177520 communique [0100]～[0101], Japanese kokai publication hei 11-133600 communique [0102]～[0103], the invention of Japanese kokai publication hei 6-16684 communique and disclosed surfactant are as suitable material.In order to obtain higher effect, any or two or more that preferably contain fluorine and be surfactant and/or silicon and be surfactant (fluorine is that surfactant or silicon are surfactant, contain the two surfactant of fluorine atom and silicon atom), most preferably fluorine is surfactant.In the situation that using fluorine to be surfactant, the fluorine-containing substituent number of fluorine atoms in this surfactant molecule is preferably 1～38, more preferably 5～25, most preferably is 7～20.If number of fluorine atoms is too much, with the common solvent phase ratio that does not contain fluorine, dissolubility reduces, and is not preferred from this viewpoint.If number of fluorine atoms is very few, can not get the uneven effect of improving, be not preferred from this viewpoint.

As particularly preferred surfactant, can enumerate the surfactant that contains following copolymer, this copolymer contains following general formula (a) and the represented monomer of general formula (b), and the mass ratio of general formula (a)/general formula (b) is 20/80～60/40.

[changing 7]

General formula (a)

General formula (b)

In formula, R ¹, R ²and R ³represent independently of one another hydrogen atom or methyl, R ⁴represent the alkyl that hydrogen atom or carbon number are 1～5.N represents that 1～18 integer, m represent 2～14 integer.P, q represent 0～18 integer, but do not comprise that p, q are all 0 situation simultaneously.

In particularly preferred surfactant, the represented monomer of general formula (a) is designated as to monomer (a), the represented monomer of general formula (b) is designated as to monomer (b).C shown in general formula (a) _mf _2m+1can be for straight chain, also can be side chain.M represents 2～14 integer, is preferably 4～12 integer.C _mf _2m+1content with respect to monomer (a), be preferably 20 quality %～70 quality %, be particularly preferably 40 quality %～60 quality %.R ¹represent hydrogen atom or methyl.And n represents 1～18, wherein preferably 2～10.R shown in general formula (b) ²and R ³represent independently of one another hydrogen atom or methyl, R ⁴represent the alkyl that hydrogen atom or carbon number are 1～5.P and q represent 0～18 integer, but do not comprise that p, q are 0 situation.P and q are preferably 2～8.

In addition,, as particularly preferred monomer contained in 1 molecular surface active agent (a), can use is the monomer of same structure each other, also can use the monomer of the different structure in the above-mentioned range of definition.This point is also same for monomer (b).

The weight average molecular weight Mw of particularly preferred surfactant is preferably 1000～40000 and then more preferably 5000～20000.Surfactant is characterised in that, it contains following copolymer: it is 20/80～60/40 that this copolymer contains above-mentioned general formula (a) and the represented monomer of general formula (b) and the mass ratio of general formula (a)/general formula (b).Particularly preferred surfactant 100 mass parts are preferably that 20 mass parts～60 mass parts, monomer (b) are that 80 mass parts～40 mass parts and other any monomer are that surplus mass parts forms by monomer (a), and then by monomer (a), are preferably that 25 mass parts～60 mass parts, monomer (b) are that 60 mass parts～40 mass parts and other any monomer are that surplus mass parts forms.

As monomer (a) and (b) in addition can copolymerization monomer, can enumerate: the Styrene and its derivatives such as styrene, vinyltoluene, AMS, 2-methyl styrene, chlorostyrene, vinyl benzoic acid, vinylbenzenesulfonic acid sodium, aminobenzene ethene, replace body; The dienes such as butadiene, isoprene; The ethene base system monomers such as acrylonitrile, vinyl ethers, methacrylic acid, acrylic acid, itaconic acid, butenoic acid, maleic acid, partial esterification maleic acid, styrene sulfonic acid maleic anhydride, cinnamic acid, ethlyene dichloride, vinyl acetate etc.

Particularly preferred surfactant is the copolymer of monomer (a), monomer (b) etc., but monomer whose sequence is not particularly limited, can for random, also can be for rule, for example can be for block copolymer, also can be graft copolymer.And then, about particularly preferred surfactant, two or more molecular structure and/or the different surfactant of monomer composition can be mixed to use.

As the content of above-mentioned surfactant, with respect to the layer total solid composition of photo-sensitive resin, be preferably 0.01 quality %～10 quality %, be particularly preferably 0.1 quality %～7 quality %.The surfactant of the ad hoc structure that surfactant contains specified quantitative and Oxyranyle and PPOX group, by containing with particular range in photo-sensitive resin, the demonstration that can improve the liquid crystal indicator that possesses this photo-sensitive resin is uneven.When its content is less than 0.01 quality % with respect to total solid composition, show that inequality can not get improving; While surpassing 10 quality %, not quite can show and show the uneven effect of improving.While containing above-mentioned particularly preferred surfactant in above-mentioned photo-sensitive resin, from the viewpoint of improvement, show that uneven is preferred.

As preferred fluorine, be the concrete example of surfactant, can enumerate the compound of recording in the section of TOHKEMY 2004-163610 communique [0054]～[0063].Can directly use following commercially available surfactant in addition.As spendable commercial surfactant, for example can enumerate: Eftop EF301, EF303 (new autumn fields changes into Co., Ltd. and manufactures), Fluorad FC430, 431 (manufactures of Sumitomo 3M Co., Ltd.), MEGAFACE F171, F173, F176, F189, F410, F444, F430, F477, F552, F553, F554, F555, F556, F557, F558, F559, F561, F562, R08, R40, R41 (Japanese ink Co., Ltd. manufactures greatly), Surflon S-382, SC101, 102, 103, 104, 105, the fluorine such as 106 (Asahi Glass Co., Ltd's manufactures) are surfactant, or silicon is surfactant.Can use in addition polysiloxane polymer KP-341 (Shin-Etsu Chemial Co., Ltd's manufacture), Troysol S-366 (manufacture of Troy KCC) is surfactant as silicon.In the present invention, being also preferably used as the fluorine that does not contain the represented monomer of general formula (a) is compound surfactant, that record in TOHKEMY 2004-331812 communique [0046]～[0052] section.

[support]

As support, be not particularly limited, can use upright and outspoken support, also can use flexible support, but the support of preferred flexible.As upright and outspoken support, be not particularly limited, can enumerate: the known glass plate such as soda-lime glass plate, low-expansion glass, alkali-free glass, quartz glass plate on surface with silica overlay film; The metallic plates such as aluminium sheet, iron plate, SUS plate; Resin plate, ceramic wafer, slabstone etc.As flexible support, be not particularly limited, can enumerate the plastic foils such as cellulose esters (such as cellulose acetate, cellulose propionate, cellulose butyrate), polyolefin (such as norbornene-based polymer), poly-(methyl) acrylate (such as polymethyl methacrylate), Merlon, polyester and polysulfones, norbornene-based polymer or paper, aluminium foil, cloth etc.From the viewpoint of processing easiness, as the thickness of upright and outspoken support, be preferably 100 μ m～3000 μ m, 300 μ m～1500 μ m more preferably.As the thickness of flexible support, be preferably 3 μ m～500 μ m, 10 μ m～200 μ m more preferably.

[oriented layer]

Stack membrane can have oriented layer.Oriented layer is brought into play following function: the differently-oriented directivity to the liquid crystal compounds in layer disposed thereon is stipulated.As long as oriented layer can be given orientation to optical anisotropic layer, can be random layer.As preferred example, can enumerate: oblique side's evaporation layer of the layer that organic compound (preferred polymers) obtains through friction treatment, passing through of take that azobenzene polymer or polyvinyl cinnamate the be representative light oriented layer that polarizing light irradiation shows liquid crystal aligning, inorganic compound and there is the layer of microflute; And ω-tricosanic acid, two (octadecyl) ammonio methacrylate and methyl stearate etc. are by the built up film of Langmuir Blodgett method (LB film) formation or the layer that dielectric generation orientation is obtained by giving electric field or magnetic field.As oriented layer, in friction mode, preferably contain polyvinyl alcohol, particularly preferably oriented layer can with its on or under it at least any 1 layer occur crosslinked.As the method that differently-oriented directivity is controlled, preferred light oriented layer and microflute.As light oriented layer, particularly preferably as polyvinyl cinnamate, can show by dimerization the layer of orientation; As microflute, the embossed of the home roll of particularly preferably making by machining or Laser Processing in advance.

[coating process]

For the composition of making each floor such as optical anisotropic layer, polymeric layer, oriented layer, can utilize dip coated method, airblade coating method, spin-coating method, slot coated method, curtain coating method, rolling method, coiling rod rubbing method, intaglio method or extrusion coated method (No. 2681294 descriptions of United States Patent (USP)) to form by being coated with.Also can be coated with two layers of above layer simultaneously.About the method being coated with simultaneously, each description and former rugged brave work コーティ Application グ engineering (coating engineering) at No. 2761791, United States Patent (USP), No. 2941898, United States Patent (USP), No. 3508947, United States Patent (USP), No. 3526528, United States Patent (USP), on the books in 253 pages of ，Chao Warehouse bookstores (1973).

[embodiment]

Enumerate embodiment below and further illustrate the present invention.Only otherwise depart from purport of the present invention, the material shown in the following examples, reagent, amount and ratio, operation etc. can be carried out suitable distortion.Thereby scope of the present invention is not limited to following concrete example.

(embodiment 1)

(heat analysis is measured the preparation with liquid T-1)

Prepare following composition, as heat analysis, measure and use liquid T-1.

[changing 8]

LC-1-1 is at room temperature solid.

(heat analysis is measured the preparation with liquid T-2)

Prepare following composition, as heat analysis, measure and use liquid T-2.

[changing 9]

LC-1-2 is at room temperature solid.

(heat analysis is measured)

Heat analysis is measured and weighed respectively 50 μ L with liquid T-1, T-2, be injected into heat and analyze with in aluminium dish.Utilize vacuum drier to be dried for standing 12 hours at 25 ℃ on aluminium dish.Aluminium dish is taken out from vacuum drier, carry out DSC mensuration.DSC is determined at from 25 ℃ and is warming up to 135 ℃, from 135 ℃, is cooled to the condition of 0 ℃ and implements.Sweep speed is 5 ℃/min.When the crystallization heat observing is evaluated, be respectively 0.60J/g, 0.15J/g in to temperature-fall period.

(preparation of coating fluid AL-1 for oriented layer)

Prepare following composition, utilize the polypropylene filter processed of aperture 30 μ m to filter, as oriented layer coating fluid AL-1.

(preparation of coating fluid LC-1 for optical anisotropic layer)

Prepare after following composition, utilize the polypropylene filter processed of aperture 0.45 μ m to filter, as optical anisotropic layer coating fluid LC-1.

(preparation of coating fluid LC-2 for optical anisotropic layer)

Prepare after following composition, utilize the polypropylene filter processed of aperture 0.45 μ m to filter, as optical anisotropic layer coating fluid LC-2.

(preparation of coating solution P-1 for polymeric layer)

Prepare after following composition, utilize the polypropylene filter processed of aperture 0.45 μ m to enter to filter, as polymeric layer coating solution P-1.

(making of stack membrane A-1)

Use coiling rod to be coated with oriented layer coating fluid AL-1 on the face of the TAC film of thickness 50 μ m, be dried, make oriented layer.The dry film thickness of oriented layer is 0.1 μ m.Next oriented layer is carried out after friction treatment, use coiling rod coating optical anisotropic layer coating fluid LC-1, at 90 ℃ of face temperature dry 2 minutes, make after liquid crystalline phase state, use the air cool metal halide lamp (manufacture of EYE GRAPHICS Co., Ltd.) of 160W/cm, irradiation ultraviolet radiation under air, by its state of orientation immobilization, forms the optical anisotropic layer of thickness 4.5 μ m.The ultraviolet illumination of now using is 600mW/cm in UV-A region (accumulation of wavelength 320nm～400nm) ², exposure is 300mJ/cm in UV-A region ².The delay of optical anisotropic layer is 400nm, at 20 ℃ of polymer that are solid.Finally use coiling rod coated polymeric layer coating fluid P-1 on optical anisotropic layer, be dried, form the polymeric layer of thickness 0.8 μ m, make stack membrane A-1.

(making of stack membrane A-2)

Except making optical anisotropic layer coating fluid, be LC-2, similarly make stack membrane A-2 with A-1.

(mensuration of the content of the liquid crystal compounds in polymeric layer)

Polymer and liquid crystal compounds are mixed in KBr, implement IR and measure, make the calibration curve of polymer and liquid crystal compounds.Utilize cutter to cut the surface of stack membrane A-1, A-2, thereby cut, get polymeric layer.By cutting the polymeric layer of getting, mix with KBr, make KBr tablet.Use KBr tablet to implement IR and measure, by determine the content of the liquid-crystal composition in polymeric layer with above-mentioned calibration curve.The content of the liquid crystal compounds in A-1, A-2 is respectively 3.0 quality %, 19.6 quality %.

(evaluation of the property separated out)

Stack membrane A-1, A-2 are applied to 2kg/cm under the state of 40 ℃ ²loading, after standing 24 hours, carry out surface state inspection Check, result is all unconfirmed to crystallization.

(comparative example 1)

(heat analysis is measured the preparation with liquid T-3)

Prepare following composition, utilize the polypropylene filter processed of aperture 30 μ m to filter, as heat analysis, measure and use liquid T-3.

(heat analysis is measured the preparation with liquid T-4)

Prepare following composition, utilize the polypropylene filter processed of aperture 30 μ m to filter, as heat analysis, measure and use liquid T-4.

(heat analysis is measured)

While similarly using T-3, T-4 to carry out the evaluation of crystallization heat with T-1, T-2, be 1.88J/g, 0.80J/g.

(evaluation of the property separated out)

(preparation of coating solution P-2 for polymeric layer)

Prepare following composition, as polymeric layer coating solution P-2.

Except making polymeric layer coating fluid, be P-2, similarly make stack membrane A-3, A-4 with A-1, the A-2 of embodiment 1.Polymer film A-3, A-4 are applied to 2kg/cm under the state of 40 ℃ ²loading, after standing 24 hours, carry out surface state inspection Check, results verification is to violent crystallization.

(mensuration of the content of the liquid crystal compounds in polymeric layer)

Utilize cutter to cut the surface of stack membrane A-3, A-4, similarly to Example 1 the content of the liquid-crystal composition in polymeric layer is determined.The content of the liquid crystal compounds in A-3, A-4 is respectively 2.6 quality %, 18.5 quality %.

Confirming, is 0.75J/g following in the situation that evaluating heat-transmission, crystallization does not occur, can preserve; On the other hand, in the situation that evaluating heat-transmission higher than 0.75J/g, owing to having there is significant crystallization, cannot preserve.

Claims

1. a manufacture method for stack membrane, it comprises:

By containing, there is polymerizable group and at 25 ℃, be the liquid crystal compounds of solid liquid crystalline composition solidifies to form layer; And by the composition that contains polymer, form polymeric layer on described layer;

After described polymeric layer forms, described liquid crystal compounds moves in described polymeric layer, until described liquid crystal compounds reaches 0.1 quality %～30 quality % with respect to the solid constituent quality of described polymeric layer;

Wherein, this manufacture method comprises selects described liquid crystal compounds and described polymer from following combination, and this is combined as take the combination below 0.75J/g of the crystallization heat of the mixture that mass ratio 9:10 is mixed to get by described liquid crystal compounds and described polymer.

2. manufacture method as claimed in claim 1, wherein, is directly coated on the described composition that contains polymer on the layer that described liquid crystalline composition is solidify to form.

3. manufacture method as claimed in claim 1 or 2, wherein, after described polymeric layer forms, described liquid crystal compounds moves in described polymeric layer, until described liquid crystal compounds reaches 1 quality %～20 quality % with respect to the solid constituent quality of described polymeric layer.

4. the manufacture method as described in claim 1～3 any one, wherein, described curing by carrying out based on light-struck polymerisation.

5. the manufacture method as described in claim 1～4 any one, wherein, described in contain polymer composition with the form of the solution of following solvents, be coated with, this solvent is selected from alkyl halide, ester, ketone, alcohol, glycol ethers or their mixture.

6. manufacture method as claimed in claim 5, wherein, the described composition that contains polymer is coated with the form of the solution of following solvents, and this solvent is selected from acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, methyl alcohol, ethanol, isopropyl alcohol, butanols, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or their mixture.

7. a stack membrane, it is manufactured by the manufacture method described in claim 1～6 any one.

8. a stack membrane, it sequentially comprises: the layer being formed by the liquid crystalline composition that contains the liquid crystal compounds with polymerizable group and the polymeric layer being formed by the composition that contains polymer, wherein,

In described polymeric layer, with respect to the solid constituent quality of described polymeric layer, the content of described liquid crystal compounds is 0.1 quality %～30 quality %;

Described liquid crystal compounds is to be the compound of solid at 25 ℃;

Described liquid crystal compounds and described polymer be take to the crystallization heat of the mixture that mass ratio 9:10 is mixed to get below 0.75J/g.

9. stack membrane as claimed in claim 7 or 8, wherein, described polymeric layer is optical isotropy layer.

10. the stack membrane as described in claim 7～9, wherein, described liquid crystal compounds is the rod shaped liquid crystal compound with 2 polymerizable groups, and described polymer is copolymer, polyester, polyurethane, polystyrene, polyvinyl alcohol, vinyl-vinyl acetate copolymer, polyvinyl chloride, the cellulose derivative of poly-(methyl) methyl acrylate, (methyl) acrylic acid and (methyl) acrylate.

11. stack membranes as described in claim 7～10 any one, wherein, described polymer has polar group or hydrophilic radical at side chain.

12. stack membranes as claimed in claim 11, wherein, described polar group or hydrophilic radical are hydroxyl or carboxyl.

13. stack membranes as described in claim 7～12 any one, wherein, the thickness of described polymeric layer is below 10 μ m.